CN104736273A - Process for the production of crystalline titanium powder - Google Patents
Process for the production of crystalline titanium powder Download PDFInfo
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- CN104736273A CN104736273A CN201380029807.1A CN201380029807A CN104736273A CN 104736273 A CN104736273 A CN 104736273A CN 201380029807 A CN201380029807 A CN 201380029807A CN 104736273 A CN104736273 A CN 104736273A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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Abstract
The invention provides a process for the production of crystalline titanium powder containing single crystals or agglomerates of single crystals having an average crystal size (by volume) greater than 1 [mu]m, said process including reacting a titanium chloride species, preferably titanium dichloride, and reducing metal in a continuous back-mix reactor to produce a free flowing suspension of titanium powder in molten chloride salt wherein: i. both the titanium chloride species and the reducing metal are dissolved in a molten chloride salt and fed to the reactor containing a chloride salt of the reducing metal; ii. the average feed ratio of the titanium chloride species and reducing metal to the continuous back-mix reactor is within 1%, preferably within 0.1%, of the stoichiometric ratio required to fully reduce the titanium chloride salt to titanium metal; iii. the concentration of titanium powder in the fluid suspension of titanium powder in molten salt in the continuous back-mix reactor is between 2 and 23 mass%; and iv. The reducing metal is lithium, sodium, magnesium, or calcium.
Description
Invention field
The present invention relates to the preparation of crystal titanium powder.
Background of invention
One of initial trial preparing titanium crystal is described in the patent (1958) by Keller and Zonis.Keller and Zonis to have recognized titanium chloride species slowly, step-by-step reduction is for the importance obtaining crystal titanium.
Keller and Zonis further highlights the importance being partially formed titanium particulate that the reducing agent that distributes equably is reduced rapidly to avoid titanium in reactant salt medium.
White and Oden describes the method for the granular Ti metal preparing not halide field trash, and it needs the stream be made up of Na, Mg, Li or K of being dissolved in the halide salts of respective metal in continuously stirred tank reactor (CSTR) is reacted with the stream be made up of the halide salt flowage of the halide salts containing Ti.Although being intended that of the method provides the condition allowing titanium ordering growth, but do not recognize the importance of the key factor reaching such condition, such as: the necessity guaranteeing the low concentration (this by by the ground charging of reactant approximate stoichiometry and the long time of staying is in the reactor provided and realizes) of the halogenated titanium of reducing metal and the dissolving of dissolving in the reactor, using the advantage of two kinds of reactive components as rare logistics charging, keep the high concentration of titanium crystal in the reactor to strengthen the growth of such titanium crystal relative to the formation of new titanium crystal core, by reducing TiCl with the excessive titanium particle be suspended in the halide salt flowage of melting
4prepare the benefit of the incoming flow containing halogenated titanium charging, with the necessity preventing the not controlled reduction of titanium chloride via long-range electron intermediary reduction (Long Range Electronically Mediated Reduction) (LR-EMR), this is described in J.Mater.Res., 13rd volume, No. 12, in December, 1998, in 3372 to 3377.And, do not recognize the necessity avoiding High Operating Temperature, High Operating Temperature can cause being formed may containing encapsulated halide salts bunch the partially sintering of titanium crystal, and the substitute is, this process teach and use High Operating Temperature to be increased in the solubility of the different reaction species in the halide salts of melting.
Difference with the prior art of the present invention is, it optimizes the combination of the multiple requirement needed for condition of reaching preparation and grown crystal titanium particle in a continuous manner.
Summary of the invention
According to the present invention, provide at the hot TiCl of continuous metal
4the method of titanium crystal and the growth of control titanium crystal is prepared in reduction process.
Therefore, according to the present invention, provide a kind of method preparing crystal titanium powder, described crystal titanium powder contains and has average crystalline size (by volume) and be greater than the monocrystalline of 1 μm or the aggregate of monocrystalline, described method comprises makes titanium chloride species, preferred titanium chloride, and reducing metal is reacted to prepare titanium powder flow freely suspension in fused chloride salt in continuous back-mix reactor, wherein:
I. described titanium chloride species and described reducing metal are all dissolved in the fused chloride salt containing the titanium powder suspended, and are fed in the described reactor of the chloride salt containing described reducing metal;
Ii. described titanium chloride species and reducing metal to the average feed rate ratio of described continuous back-mix reactor in completely chlorination titanium salt is reduced into the stoichiometric proportion needed for titanium 1%, preferably in 0.1%;
Iii., in described continuous back-mix reactor, in the fluid suspension of titanium powder in fuse salt, the concentration of described titanium powder is between 2 to 23 quality %; And
Iv. described reducing metal is lithium, sodium, magnesium or calcium.
Some fuse salts can be taken out together with titanium powder product from described continuous back-mix reactor, and outer separated from one another at described reactor.
The charging of dissolving chlorination titanium species can be prepared, preferably by making TiCl in the independently container outside described continuous back-mix reactor
4react with the Titanium be dispersed in fused chloride salt recycled from described continuous back-mix reactor and prepare.
Can by described reducing metal before being fed to described continuous back-mix reactor predissolve in fused chloride salt, preferably by fuse salt being recycled to container from described continuous back-mix reactor and in this embodiment described reducing metal being dissolved in described chloride salt and carrying out.
The container preparing the chlorination titanium salt of described dissolving and the reducing metal of described dissolving can be electrically insulated from each other, and with described continuous back-mix reactor electric insulation.
The cationic molar concentration of titanium of the dissolving of described chlorination titanium salt can be less than 25% of the molar concentration of the cl anion in described fuse salt feedstock solution, is preferably less than 5%.
The molar concentration of the reducing metal atom of the dissolving in the charging of described fused chloride salt can be less than 3.5% of the described cl anion of molten salt solution, is preferably less than 0.5%.
The reducing metal of dissolving can exceed the stoichiometry needed for the whole low price titanium chlorides for reducing in the described charging of described continuous back-mix reactor to the charging of described continuous back-mix reactor.
The temperature of described continuous back-mix reactor can lower than 800 DEG C, typically lower than 700 DEG C, preferably lower than 650 DEG C.
The time of staying in described reactor can be expressed as the volume of the titanium powder in described continuous back-mix reactor inside and the ratio of the volumetric rate of the titanium powder prepared in described continuous back-mix reactor, and five minutes can be greater than, be preferably greater than 20 minutes.
The titanium being recycled to the dispersion of the described container of the halogenated titanium species preparing described dissolving is relative to by described TiCl
4the charging stoichiometry be reduced into completely needed for titanium chloride can be excessive.
Benefit of the present invention
At TiCl
4titanium blocking in feeding line can be formed through the LR-EMR of the titanium chloride species of reducing metal (Li, Na, Mg or Ca).This can pass through first by TiCl
4be fed to prereduction reactor to be prevented, prereduction reactor is not fully reduction, thus does not cause any titanium chloride species to be reduced to titanium.
When use reducing metal is as alkali or alkaline-earth metal reduction TiCl
4during to prepare subchloride, if it is possible that use excess reducing metal, if or free alkali or alkaline-earth metal with contact TiCl
4the metal structure of import contacts, then can form titanium.When with Titanium reduction titanium chloride species, only can form the low price titanium chloride compared with lower valency.
This method can comprise destroys first stage TiCl
4electrical contact between prereduction district, final reducing zone and/or reducing agent dissolve area and/or salt bridge, otherwise, if any regional Electronic and ion coupling that there is alkali or alkaline-earth metal in first stage prereduction reactor and whole process, then titanium tetrachloride and at a low price titanium chloride can occur via LR-EMR to the electrochemical reduction of titanium.
By LR-EMR effect, the agglomerate of the titanium sponge adhering to reactor wall or inside also can be caused.This situation can acutely reduce, and condition destroys between undissolved reducing metal and reactor wall and the electrical contact of inside, to prevent the electron stream to the region containing low price titanium chloride.In theory, the reducing metal of dissolving also can cause the formation of titanium sponge, but the low multiple order of magnitude of Conductivity Ratio melting and reducing metal of fuse salt containing the reducing metal of dissolving, therefore (or dispersion) reducing metal making to dissolve does not become problem.
The concentration of the reducing metal of dissolving can specially keep operating under low condition by final low price titanium chloride reduction phase.The concentration of reducing metal is lower, and the chemical driving force formed for titanium is lower, and also lower to the electrical conductivity of the contributive fuse salt of electrical contact between the reducing metal of dissolving and the metal of structure reactor.
TiCl
4cationic for the titanium of dissolving concentration can specially keep operating under low condition by pre-reduction stage and final low price titanium chloride reduction reactor.The cationic concentration of titanium of dissolving is lower, lower for the chemical driving force forming titanium.The low price titanium chloride being dissolved in the remnants in reaction medium is undesired in the titanium products recycling step of downstream, because can pollution products it forms titanium dioxide, hydrochloric acid and hydrogen during reacting with water.
Titanium crystallization reactor operates under can there is the condition of the titanium crystal of the suspension of high concentration wherein in fuse salt.When need not add be fed to the salt dilution of titanium crystallization reactor, maximum accessible be the chlorion of titanium/tetra-of 1 mole in salt mole.Preferably should avoid dilution or minimize dilution.Crystal growth rate is directly proportional to the total surface area of the crystal existed in reactor; Therefore the existence of crystal adds the forming rate of crystals relative to crystal nucleation.And the existence of the titanium particle of suspension enhances the possibility of crystal titanium formation.Have a mind to keep kind of an existence for crystalline substance to be vital practice in reactive crystallization, wherein, kind is brilliant plays the effect obviously reducing reagent local concentration, and maintenance kind of brilliant existence provides the crystal growing surface for the nucleation of fine particle intentionally.Introduce the key that kind of brilliant (seeding) is considered to the control of reaching reaction crystallization process, when not introducing kind brilliant, excessive nucleation will occur, and final granularity can critical constraints.
Can approximate stoichiometry ground (or as far as possible close to stoichiometric proportion) by used for this method two gangs of incoming flow (TiCl
4and reducing metal) be fed in this technique.In practice, this will at 0.5% excess reducing metal and 1% excessive TiCl
4between.When charging and the long residence time of precise stoichiometry, in final titanium chloride reduction reactor at a low price, the titanium cation of dissolving and the concentration of reducing metal atom will become very low, and close to thermodynamical equilibrium.As depicted, low concentration (close to zero) is conducive to crystal growth for crystal nucleation.Can add and use known method in reactive crystallization field to strengthen particle or crystal growth, as, by the recirculation of a large amount of kinds crystalline substance, near the eyelet of the impeller for stirred reactor, CSTR (continuously stirred tank reactor (CSTR) is introduced in incoming flow, also referred to as Continuous Flow stirred tank reactor, or be called continuous backmixed reactor), the power of agitator of increase, or dissimilar agitator design or ultrasonic agitation.
Final low price titanium chloride reduction reactor can approximate stoichiometry but under there is the condition of reducing metal excessive a little operation and control.Operate final low price titanium chloride reduction reactor by approximate stoichiometry, the concentration of the reducing metal of titanium cation and dissolving can be minimized.When the titanium cation dissolved is reduced, the titanium atom of unstable dissolving can be formed, and these atoms or be bonded to each other and form new titanium core, or the titanium crystal existed can be bonded to, thus form larger crystal.By the concentration of the species of lower formation crystal, increase the crystal growth rate relative to nucleation rate.Therefore think, more favourable than other various methods at the reducing metal concentration operation titanium crystallizer of lower titanium cation concn and slightly high dissolving.
The effect of the low price titanium chloride of the remnants of reduction of dissolved in reaction medium also will be played in reducing metal excessive a little, remaining low price titanium chloride is undesired in downstream titanium products reclaims, because can pollution products it forms titanium dioxide, hydrochloric acid and hydrogen during reacting with water:
The time of staying in final low price titanium chloride reduction reactor must be fully long, to guarantee the particle wanted or crystal growth, as discussed above, typically is at least 5 minutes.The time of staying is in the reactor longer, the reducing metal of dissolving and the cationic ultimate density of titanium lower.These concentration are lower, and crystal growth is higher than the relative speed of crystal nucleation.But the time of staying is longer, reactor is larger, and it is larger to the rapid mixing difficulty in reactor content to obtain incoming flow.Determining the desirable time of staying relative to reactor size and recirculation flow.
Before reducing metal can be dissolved completely in the concentration lower than 1 molar percentage and preferably lower than 0.4 % by mole to be fed in the salt of final low price titanium chloride reduction reactor (but, the entrained drip of reducing metal can exist, but should be minimized).In view of any actual response container desirable, be perfectly blended in and can not reach in theory, and the reactor time of staying more greatly or in the reactor longlyer becomes difficulty further, and the regional area of high reactant concentration will cause the transition nucleation of titanium particle.And, at melting MgCl
2the solubility of middle magnesium is only about 0.15 % by mole, and the solubility of Li is about 0.5 % by mole in LiCl.Therefore, when not obvious lifting technique temperature, higher reducing metal can not be obtained and be dissolved in concentration in their chloride salts, and when sodium, this is easily close to the boiling point of metal.This feature has advocated a kind of so method, described method with wherein in order to higher output increases compared with the prior art of reagent concentration, operate at lower temperature and concentration.
Large to TiCl
4the recirculating mass of prereduction reactor and reducing metal dissolving step may be used for the incoming flow of diluting final low price titanium chloride reduction reactor.The cationic concentration of titanium in from the charging to final low price titanium chloride reduction phase also can reduce in fact feasible so much.Preferably, must there is the titanium cation (Ti be dissolved in salt being less than a mole in the cl anion of every four moles in salting liquid
2+or Ti
3+).Preferably, this ratio must be less than 1: 8, and more preferably, it should be less than 1: 16 (ratio to be validated).In addition, particularly when using sodium or calcium as reducing metal, the recirculation flow to reducing metal dissolution phase is preferably increased, to reduce the concentration of sodium or calcium.
The metal concentration dissolved in charging when use sodium or calcium are as should preferably lower than 2 % by mole during reducing agent, when using lithium lower than 0.5 % by mole, and when use magnesium as during reducing metal lower than 0.15%.
Excessive titanium particle or crystal can be recycled to first stage TiCl
4prereduction reactor.Titanium cation (Ti
2+and Ti
3+) in some may be adsorbed on the surface of excessive titanium crystal.When being reintroduced back to by these particles to final low price titanium chloride reduction phase, be contemplated that by the cation adsorbed it is not form new titanium core, but will be bonded on the titanium crystal existed that they adsorb when being reduced.
The low price titanium chloride reduction phase that so low temperature operation that can be feasible is actually final.Except the problem of the standard difficulty of corrosion and similar adjoint high-temperature process, the further problem of the temperature of adjoint rising is the sintering of titanium particle, its can cause in salt under the existence of fuse salt some be encapsulated in the space of the aggregate of sintering.Need not expensive melting operation even if just to remove this salt from particle be not impossible, that is also very difficult, and the strict demand that therefore preparation has a titanium powder of very low chloride content becomes difficulty (such as 0.005 quality %).
There is not the accurate temperature that titanium crystal starts to sinter, in the temperature from 750 DEG C, significantly sintering occurs although reported.When not adding other chloride salt to form eutectic mixture, the absolute minimum temperature that this method can be run is the fusing point of the chloride salt of reducing metal.The respective fusing point being considered to the chloride salt of four kinds of reducing metals the most feasible is: be 610 DEG C for LiCl, is 801 DEG C, for MgCl for NaCl
2be 714 DEG C, and for CaCl
2it is 775 DEG C.In practice, minimum operation temperature is higher than salt fusing point 20 DEG C.Can find out, from by minimized for sintering viewpoint, lithium is most suitable reducing metal, and magnesium is second-best (higher temperatures of about 104 DEG C).
At first stage TiCl
4excessive titanium particle can be there is in prereduction reactor.Although TiCl
3tiCl is formed with Fe
2and FeCl
2reaction be not very well (favourable), but at typical operating temperature of the present invention, reaction product can be dissolved in the existence of fuse salt wherein under, it becomes more smooth.This can cause the excessive pollution of titanium products.In order to reduce the degree of iron pollution, TiCl must be made by having free Titanium particle in salt
3tiCl is formed by Ti reduction
2, thus reduce TiCl
4the oxidation potential of the content of prereduction reactor.TiCl
2compare TiCl
3oxidisability is much lower.
At first stage TiCl
4in prereduction reactor, the specially maintenance of free metal titanium particle can be recycled via by the titanium products from terminal stage reduction reactor or be completed via interpolation titanium (such as leftover pieces).
This method can be feasible actually so low temperature operation.Temperature is lower, and the speed of the oxidation of iron is lower, and with the TiCl dissolved in fuse salt
3by Fe forms to form the FeCl dissolved
2thermodynamic driving force lower.
Lower temperature limiting salt evaporation.The mineralization evaporated in the high-temperature part of reactor, in the comparatively cold-zone section (namely in waste line) of reactor, causes blocking.The measurement must carrying out adding is to remove these deposits.The vapour pressure valuation of 20 DEG C on the fusing point of salt of different chloride salts provides in Table 1.
Table 1: the salt vapour pressure of 20 DEG C on salt fusing point
Can find out, from making salt evaporate minimized viewpoint, calcium is best reducing metal, and lithium is second-best reducing metal.
So low temperature operation this method that can be feasible actually, to limit the steam of reducing metal.The steam of reducing metal causes danger, wherein it can uncontrollably with the TiCl being in vapor phase
4reaction, causes temperature out of control.The vapour pressure valuation of 20 DEG C on the fusing point of respective salt of different reducing metals provides in table 2.
Table 2: the metal steam air pressure of 20 DEG C on chloride salt fusing point
Can find out, from making reducing metal evaporate minimized viewpoint, lithium is up to the present best reducing metal, and calcium is second-best reducing metal.
Embodiment of the present invention describes
Now with reference to illustrative graphic block diagram, the present invention is discussed, described block diagram is not intended to limit the scope of the invention.
In the block flow diagram that titanium synthesis is described, above figure, show a part for CSIR-Ti process.In fact, TiCl is reduced continuously with two stages
4, first in pre-reduction stage, make TiCl
4react to form the low price titanium chloride be dissolved in fuse salt with Ti, and the final reduction phase forming titanium is reacted in the reducing metal of the low price titanium chloride dissolved and dissolving.End reaction device is operated as CSTR.End reaction device also can classify as reactive crystallizer because two kinds dissolve reactant in the reactor fast reaction form insoluble titanium particle.
Three plumes leave reactor.First plume is sent to reducing metal dissolution vessel, and reducing metal wherein to be used was dissolved in this stream before it being recycled to final subchloride reduction reactor.Another plume containing partial suspended titanium particle is made to be sent to first stage TiCl
4reduction reactor, partly will be fed to the TiCl in technique
4reduction.Final stream by chilling, and is sent to downstream process, to be separated from salt by titanium products and to reclaim salt (not shown) when it being removed from reactor subsequently.
It is believed that described method overcomes or reduces some or all in following problem:
TiCl
4the blocking of feeding line
In the formation of inside reactor titanium agglomerate.
On average be greater than the growth of the elementary titanium particle of 5 microns.Less particle is suitable for powder metallurgy unsatisfactoryly, and the relative size of passivation oxygen layer is equal to high oxygen contamination level.
The sintering of titanium particle.Chloride content is extremely important in Downstream processing; Salt may be encapsulated and make powder infeasible in many purposes by sintering.
The corrosion of inside reactor.
Salt evaporates.
The evaporation of reducing metal.
Claims (19)
1. prepare the method for crystal titanium powder for one kind, described crystal titanium powder contains average crystalline size (by volume) and is greater than the monocrystalline of 1 μm or the aggregate of monocrystalline, described method comprises to be made titanium chloride species and reducing metal in continuous back-mix reactor, react to prepare titanium powder to flow freely suspension in the chloride salt of melting, wherein:
I. described titanium chloride species and described reducing metal are all dissolved in fused chloride salt, and are fed in the described reactor of the chloride salt containing described reducing metal;
Titanium chloride species described in ii and reducing metal to the average feed rate ratio of described continuous back-mix reactor in completely chlorination titanium salt is reduced into the stoichiometric proportion needed for titanium 1%;
Iii., in described continuous back-mix reactor, in the fluid suspension of described titanium powder in fuse salt, the concentration of titanium powder is between 2 to 23 quality %; And
Iv. described reducing metal is lithium, sodium, magnesium or calcium.
2. some fuse salts wherein, are taken out by the method described in claim 1 together with titanium powder product from described continuous back-mix reactor, and outer that they are separated from one another at described reactor.
3. the method described in claim 1 or claim 2, wherein, prepares the described charging of the titanium chloride species of described dissolving in the independently container outside described continuous back-mix reactor.
4. the method described in claim 3, wherein, in the independently container outside described continuous back-mix reactor, the described charging of the titanium chloride species of described dissolving is by making TiCl
4react with the Titanium be dispersed in fused chloride salt recycled from described continuous back-mix reactor and prepare.
5. the method described in any one of front claim, wherein, by described reducing metal before being fed to described continuous back-mix reactor predissolve in fused chloride salt.
6. the method described in claim 5, wherein, by fuse salt is recycled to container from described continuous back-mix reactor, said reducing metal is dissolved in described chloride salt, thus by described reducing metal before being fed to described continuous back-mix reactor predissolve in fused chloride salt.
7. the method described in any one of front claim, wherein, the container for the preparation of the chlorination titanium salt of described dissolving and the reducing metal of described dissolving be electrically insulated from each other and with described continuous back-mix reactor electric insulation.
8. the method described in any one of front claim, wherein, in described fuse salt feedstock solution, the cationic molar concentration of titanium of the dissolving of described chlorination titanium salt is less than 25% of the molar concentration of cl anion.
9. the method described in claim 8, wherein, the cationic molar concentration of titanium of the dissolving of described chlorination titanium salt is less than 5% of the molar concentration of the cl anion in described fuse salt feedstock solution.
10. the method described in any one of front claim, wherein, the molar concentration of the reducing metal atom of the dissolving in the chloride salt charging of described melting is less than 3.5% of the described cl anion of described molten salt solution.
Method described in 11. claims 10, wherein, the molar concentration of the reducing metal atom of the dissolving in the chloride salt charging of described melting is less than 0.5% of the described cl anion of described molten salt solution.
12. methods described in any one of front claim, wherein, the described charging to described continuous back-mix reactor of the reducing metal of dissolving exceedes the stoichiometry needed for the whole low price titanium chloride reduction in the described charging to described continuous back-mix reactor.
13. methods described in any one of front claim, wherein, the temperature of described continuous back-mix reactor is less than 800 DEG C.
Method described in 14. claims 13, wherein, the temperature of described continuous back-mix reactor is less than 650 DEG C.
15. methods described in any one of front claim, wherein, the time of staying in described reactor is expressed as the volume of the titanium powder in described continuous back-mix reactor inside and the ratio of the volumetric rate of the titanium powder prepared in described continuous back-mix reactor, and is greater than five minutes.
Method described in 16. claims 15, wherein, the time of staying in described reactor is expressed as the volume of the titanium powder in described continuous back-mix reactor inside and the ratio of the volumetric rate of the titanium powder prepared in described continuous back-mix reactor, and is greater than 20 minutes.
17. methods described in any one of front claim, wherein, the titanium being recycled to the dispersion in the described container of the halogenated titanium species preparing described dissolving is relative to by TiCl
4the charging stoichiometry be reduced into completely needed for titanium chloride is excessive.
18. methods described in any one of front claim, wherein, described titanium chloride species are titanium chloride.
19. methods described in any one of front claim, wherein, described titanium chloride species and reducing metal to the average feed rate ratio of described continuous back-mix reactor in chlorination titanium salt is reduced into completely the stoichiometric proportion needed for titanium 0.1%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA201204134 | 2012-06-06 | ||
| ZA2012/04134 | 2012-06-06 | ||
| PCT/ZA2013/000038 WO2013185153A2 (en) | 2012-06-06 | 2013-05-29 | Process for the production of crystalline titanium powder |
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| Publication Number | Publication Date |
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| CN104736273A true CN104736273A (en) | 2015-06-24 |
| CN104736273B CN104736273B (en) | 2018-05-01 |
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| CN201380029807.1A Expired - Fee Related CN104736273B (en) | 2012-06-06 | 2013-05-29 | The preparation method of crystal titanium powder |
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| US (1) | US9567690B2 (en) |
| EP (1) | EP2844411B1 (en) |
| JP (1) | JP6216372B2 (en) |
| KR (1) | KR20150029624A (en) |
| CN (1) | CN104736273B (en) |
| AU (1) | AU2013270660B2 (en) |
| CA (1) | CA2875677A1 (en) |
| RU (1) | RU2635587C2 (en) |
| SA (1) | SA113340609B1 (en) |
| UA (1) | UA115784C2 (en) |
| WO (1) | WO2013185153A2 (en) |
| ZA (1) | ZA201500009B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185592A (en) * | 2020-02-24 | 2020-05-22 | 北京科技大学 | Method for preparing high-performance powder metallurgy titanium and titanium alloy products by solid-phase deoxidization |
| CN113747988A (en) * | 2019-04-29 | 2021-12-03 | 全球先进金属美国股份有限公司 | Ti-Zr alloy powder and anode comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10245642B2 (en) * | 2015-02-23 | 2019-04-02 | Nanoscale Powders LLC | Methods for producing metal powders |
| MX2018001923A (en) * | 2015-08-14 | 2018-08-16 | Coogee Titanium Pty Ltd | Method for production of a composite material using excess oxidant. |
| WO2017027916A1 (en) | 2015-08-14 | 2017-02-23 | Coogee Titanium Pty Ltd | Methods using high surface area per volume reactive particulate |
| EP3334848A4 (en) | 2015-08-14 | 2018-06-27 | Coogee Titanium Pty Ltd | Method for recovery of metal-containing material from a composite material |
| RU2729691C2 (en) * | 2018-12-05 | 2020-08-11 | ООО "Современные химические и металлургические технологии" (ООО "СХИМТ") | Method of aluminothermic production of metal powders and device for its implementation |
| KR102260400B1 (en) | 2019-12-27 | 2021-06-03 | 고등기술연구원연구조합 | MANUFACTURING METHOD OF Ti POWDER AND MANUFACTURING APPARATUS THEREOF |
| US11440096B2 (en) | 2020-08-28 | 2022-09-13 | Velta Holdings US Inc. | Method for producing alloy powders based on titanium metal |
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| CN1812859A (en) * | 2003-07-04 | 2006-08-02 | 联邦科学和工业研究组织 | A method and apparatus for the production of metal compounds |
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| JP2008308738A (en) * | 2007-06-15 | 2008-12-25 | Osaka Titanium Technologies Co Ltd | METHOD FOR MANUFACTURING METAL Ti OR Ti ALLOY |
| WO2011106804A1 (en) * | 2010-02-25 | 2011-09-01 | Csir | Titanium powder production process |
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- 2013-05-29 CA CA2875677A patent/CA2875677A1/en not_active Abandoned
- 2013-05-29 JP JP2015516293A patent/JP6216372B2/en not_active Expired - Fee Related
- 2013-05-29 UA UAA201412750A patent/UA115784C2/en unknown
- 2013-05-29 RU RU2014147781A patent/RU2635587C2/en active
- 2013-05-29 US US14/406,166 patent/US9567690B2/en active Active
- 2013-05-29 CN CN201380029807.1A patent/CN104736273B/en not_active Expired - Fee Related
- 2013-05-29 KR KR1020147033347A patent/KR20150029624A/en not_active Application Discontinuation
- 2013-05-29 WO PCT/ZA2013/000038 patent/WO2013185153A2/en active Application Filing
- 2013-05-29 EP EP13756987.7A patent/EP2844411B1/en active Active
- 2013-05-29 AU AU2013270660A patent/AU2013270660B2/en not_active Ceased
- 2013-06-01 SA SA113340609A patent/SA113340609B1/en unknown
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2015
- 2015-01-05 ZA ZA2015/00009A patent/ZA201500009B/en unknown
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| US5259862A (en) * | 1992-10-05 | 1993-11-09 | The United States Of America As Represented By The Secretary Of The Interior | Continuous production of granular or powder Ti, Zr and Hf or their alloy products |
| CN1812859A (en) * | 2003-07-04 | 2006-08-02 | 联邦科学和工业研究组织 | A method and apparatus for the production of metal compounds |
| CN101142330A (en) * | 2005-03-15 | 2008-03-12 | 住友钛株式会社 | Method of high-melting-point metal separation and recovery |
| JP2008308738A (en) * | 2007-06-15 | 2008-12-25 | Osaka Titanium Technologies Co Ltd | METHOD FOR MANUFACTURING METAL Ti OR Ti ALLOY |
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| CN113747988A (en) * | 2019-04-29 | 2021-12-03 | 全球先进金属美国股份有限公司 | Ti-Zr alloy powder and anode comprising same |
| CN113747988B (en) * | 2019-04-29 | 2023-10-20 | 全球先进金属美国股份有限公司 | Ti-Zr alloy powder and anode containing same |
| CN111185592A (en) * | 2020-02-24 | 2020-05-22 | 北京科技大学 | Method for preparing high-performance powder metallurgy titanium and titanium alloy products by solid-phase deoxidization |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2635587C2 (en) | 2017-11-14 |
| CN104736273B (en) | 2018-05-01 |
| ZA201500009B (en) | 2017-09-27 |
| US20150144055A1 (en) | 2015-05-28 |
| WO2013185153A3 (en) | 2014-03-06 |
| JP2015525295A (en) | 2015-09-03 |
| AU2013270660A1 (en) | 2014-12-18 |
| RU2014147781A (en) | 2016-07-27 |
| US9567690B2 (en) | 2017-02-14 |
| AU2013270660B2 (en) | 2017-09-21 |
| EP2844411A2 (en) | 2015-03-11 |
| KR20150029624A (en) | 2015-03-18 |
| SA113340609B1 (en) | 2015-11-10 |
| UA115784C2 (en) | 2017-12-26 |
| EP2844411B1 (en) | 2017-09-27 |
| CA2875677A1 (en) | 2013-12-12 |
| WO2013185153A2 (en) | 2013-12-12 |
| JP6216372B2 (en) | 2017-10-18 |
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